Sulphocarboxylic esters



No Drawing. No.

a. Harris, Chicago, an.

Application August 5, 1935, Serial 34,840. Renewed January 23, 1939 8 Claims. (Cl; 2605-400) My invention relates to a new class of chemiclass of chemical substances particularly adapted for use as detergents,'wettlng, penetrating, lath-.

ering, flotation and anti-smttering agents, and for frothing purposes. a y

In certain classes of industries, there is a. need for a certain class of chemical substances usually used in relatively small quantities but capable of use in larger quantities to secure an efiect principally the result of awetting action such as at a water-oil interface? In the textile and dyeing industries, for'example, there are many situations where a wetting or detergent action is imperative and many difierent chemical substances have been produced calculated to reduce surface tension and promote wetting in these industries. The use of prior art substances has not been attended with unqualified; success in all instances.

. In certain other types of industries, such as the margarine industries, for example, problems in preventing the spattering of margarine in frying have arisen. These problems are considered .by some investigators as entirely a matter of wetting; in other words, by promoting greater attraction between the oleaginous and aqueous por-. tions of the emulsion at the interfaces thereof. Although the problem is probably not one of wetting action entirely, it appears that certain compounds which in theory tend to concentrate at the water oil interface will have an-eiiect upon the spattering behavior of margarine. This problem is discussed and a remedy disclosed in my co-pendingl application, Serial No. 566,156, filed September 30, 1931, now Patent No. 1,917,256, 'as a continuation-impart of a priorapplication,

Serial No. 475,622, new Patent No. 1,917,250.

The principal object of my present invention isthe provision of a new class of chemical substances capable of satisfactory use in connection with the problems hereinabove discussed.

Another object is the provision of a new class of chemical substances which are in general of relatively simple structure and can be cheaply made incommercial quantities.

Another object isthe provision ofa class of chemical substances of the character set forth which in the main will be innocuous and nontoxic, even though employed in such foods as margarine.

Another object is the provision of a new class of chemical substances having improved wetting characteristics.

Other objectsand features of-the invention will be apparent from a consideration of the following detailed description.

The substances of my invention are in general ester derivatives of lower molecular weight fatty acids with at least one unesterlfled sulphonic acid group in the fatty acid radical wherein the group esterified with the fatty acid has a lipophile radical with at least four carbon atoms. In certain circumstances there may be more than one unesterified sulphonic acid group in the fatty acid radical orthere may be sulphonic acid groups that are esterified and other sulphonic acid groups that are not esterified, but, in all cases there must be at least one unesterified sulphonic acid group in the fatty acid radical. The fatty acidradical with the free sulphonic acid group is of relatively low molecular weight and should contain not more than eight carbons.

Y Considering the compounds from another aspect, the molecule in each instance contains a relatively high molecular weight lipophile group and a relatively low molecular weight hydrophile group which, in the class of compounds to which my present invention relates, are sulphonic acid radicals. From still another angle, the compounds may be considered'as combinations of a higher molecular weight lipophile group and a relatively low molecular weight sulpho-fatty acid group. A more complete understanding of what may comprise the lipophile group and the particular character of the sulpho-fatty acid group will be had as the detailed description progresses.

The function of the sulphonic acid group is to impart hydrophilic properties; that is, water wetting or water attracting properties, to the molecule as a whole. The groups which are esterified by the sulphonic fatty acid are in general of a lipophile character. At' times they may be strongly lipophilic and at other times moderately lipophilic. They may be of low'molecular weight o. H,cocnna n on O H: O- -CHr-S:O

' om Monostearin sulphoacctate (sodium salt) It is evident that in the substance represented above, the group which is esterified by the sulpho acetic acid happens to have a hydrophilic radical of its. own, namely the unesterified hydroxy radical in the glycerol residue.

The lipophile groups. entering into the molecular structure of my substances may be of simple character, as, for example, in sulphoacetates of cetylalcohol, oleyl alcohol, dodecenol and other straight chain aliphatic higher alcohols, or they may be of a more complex character as indicated by the substance, the structural formula of which is written directly below.

\ o H,- O-GCHr-!=O 6N: cam other of monostearln sulphoacototo (sodium salt) Some additional examples of members of the groupot substances which I have discovered are as follows:

0 HaOO- -UnHI n 'on 1 o o m -0-$- oms:o

' om Monoiam'in sulphoaeetate (sodium salt) Hic-o-cnHa I m -o- -cnr-om-s%o ONa Oetyi ethylonaglyeol sulphopmplonate (sodium salt) CH:(OHxJ1-O -CHIS O ONs Octyl sulphomtate (sodium salt) OK Butyl diothyloneslycol sulphoacetato (potamium salt) 0 H|C--0- CuH:r

0 B, -o- -on-cnr-cm 0 0 ONa Monopalmifln miphobntynh (sodium salt) 0 mc-o-Loms Mono-palmiflc sold an: o! othyk noglywl sdiphopmpiomu (sodium 0 mc-o- -ouna 0 HI -o- -cmso 0N8 Diaulphowotio acid ester of mono-01cm (disodlum salt) Mono-palmltl mold and o! tri-moth lone 001 mi inc-mute 6 (sodium salt; my D m-stcorio, fi-benzoic, niuiphoaeofl o acid ester of glycerol (sodium all) m -oJL-cn-cm Monoctoorlo add new of dama n mm: "mm mm HI O"'OHI-OHI O O OHIE%O 0N: Mono-olnio acid estuol duh 1: 23 drool niphoacohts (Indium om 01-31- lulbhoaoohh (sodium salt) arsenal ens-(cmu-cn-cns-cmcn-(onci-em-o- -cm-s20 H OK Ricinoleyl sulphoscetato (potassium salt) Generally speaking, I may select many dinerent types of compounds as lipophile groups, principally compoundshaving lipophile radicals of relatively high molecular weight. For example, the following materials may be utilized as sources of lipophile groups: hydroaromatic acids such as abietic acid, saturated and unsaturated higher aliphatic acids such as the higher fatty acids and including melissic acid, stearic acid, oleic acid, ricinoleic acid, linoleic acid, lauric acid, palmitic acid, hydro-aromatic alcohols such as abietol, .unsaturated higher all-cyclic alcohols such as the sterols, for example, cholesterol, higher unsaturated aliphatic alcohols cong at least six and preferably from nine to eighteen carbon atoms and even more, such as oleyl alcohol, ricinoleyl alcohol, palmitolcyl alcohol, dodecenol, sperm oil alcohols, etc., moncstcaryl glycerine (monostearine, so called), ny her molecular weight esters with cste'riflable hydroxy groups and other substances with marked tfii t for oils and fats. The alcohols may be prepared in any of several methods known to those smiled in the art. For example, the higher unsaturated allphatic alcohols can be prepared by the venult method.

From a. study of the compounds which I list hereinabovc, those skilled in the art will understand that I may use many diiierent cents for forming the compoundsinsoiar as the dominant lipophile group and the relatively low mo lecular weight sulpho-fatty acid group are con cerned. In general, however, ester or ether linlr ages are utilized between these two portions of the compound, and the skilled chemist will understand in general the most approved practices in securing this result. Numerous methods are also available for the introduction of the sulphonic acid group. In the case of aromatic sulphonic acids, of course, standard sulphonation procedures employed for producing aromatic sulphonic acids may be used, and, if desired, the lipophile group may be introduced subsequently.

In the case of aliphatic sulphonic acids, and for that matter, even for the production of aromatic sulphonic acids, a reactive halogen may be caused to react with sodium sulphite or potassium sul phite or ammonium sulphite or some other sul phite in aqueous solution, if desired.

Another method is to introduce a sulph-hyl or disulphide or some other suitable sulphur group and then oxidize to the sulphonic acid with nitric acid or a permanganate-or some. other oxidizing agent. v I

As an example of one of these methods, I de= scribe herewith the preparation of the sodium salt of 'cholesteryl sulphoacetate; nine parts of cholesterol, nine parts of brom acetyl bromide,

- and forty parts of benzene were heated under a reflux condenser for two hours at the boiling point of the mixture. The reaction ture was then washed repeatedly with hot water until it was substantially free of acid and freed of hen-- zene by distilling from a steam bath. Seven parts of this reaction product were then treated with jeven parts of sodium sulphite (NazSO's), disolved in forty parts of hot water, for five hours at the temperature of boiling water and with con-- tinuous, vigorous agitation. This reaction mixture was washed several times with hot brine until free of sulphites, dried and it it purified by extracting the impurities with dry ethyl ether. Analysis showed that the product was the sodium salt of cholestcryl sulphoacetate in relatively pure form, with an admixture of sodium chloride.

The preparation of oleyl sulphoac'etate is accomplished in substantially identically the same. manner as described above for the preparation of cholesteryl sulphoacetate. In; this case, ten

parts of oleyl alcohol may be reacted with ten parts of brain acetyl bromide, the rest of the conditions described above being essentially the same.

Those skilled in the art are. referred to my Patent No. 1,917,260, in which I disclose the use of some 'of the compounds of my present invention as anti-sputtering agents for use in mar-- garine. In this patent, I also treat of the manner of making some of these compounds.

Those oil my substances which are freely soluble in water may be recovered from their solotions and from their water. solutions in the customery manner by concentrating and crystallizing. As stated hereinabove, as the mass of the lipophile radical increases, solubility decreases and amnity .for water is manifested by the dispersibility in water. From these dis'perslons,-my substances may be readily recovered by .s altlng out with suitable soluble electrolytes. qommon salt is very satisfactory for this purpose'in most c. salted out of an aqueous dispersion at temperatures ranging from to 95 6., the substances are obtained in the form of a paste with a water content. ranging from approximately 25 to The more hydrophflic the substance, the greater the water content, and,

of course, the salt is present in the water of many respects dltfering from each other in accordance with the numerous examples given,

nevertheless may all be represented-by the structural formula wherein "R." is the lipophile group, X is the carbon-hydrogen residue of the sulpho-iatty acid, "Y" is a cation, and "w" is a small whole number, at lewt one.

I have previously referred to the fact that the lipophile group may in itself contain hydrophile rcals. For example, in the case oi monostearin sulpho-acetate, the hydroxy radical of the second glycerine carbon has a recognized hydrophilic character. 'Thegroup as a. whole, however, of which this hydroxy radical is a part, is dominantly lipophile, the single hydroxy radical in such a compound being insuiilcient to impart dominant hydrophile characteristics to the group as a whole. Moreover, in the case of a compound having an esterified sulphonic acid group, this s-ulphonic acid group will usually be found topossees a lipophile character or at least will not have a marked hydrophile character due'to'the additional group or radical which has been attached to the sulphonic acid group by esteriflcation.

When the character R. is used in the formula, therefore, to represent a, llpophile group, it is Considering more specifically the character of the lipophile group, it will at once be apparent that for the most part I employ derivatives of glycerol or glycols, although the lipophile group.

may comprise a straight chain higher molecular weight fatty acid group suitably attached to the sulpho-fatty acid of relatively low molecular weight. Insofar as the sul'pho-fatty acid group is concerned, I may employ a sulpho-actate, sulpho.

groups or in other words no part of the'com-' pound is in the form of an ester of sulphuric acid, The numerous examplesgiven are clear.

in this feature.

My present application is a continuation-inpart 01. my copending application, Serial -No.

627,096, filed July 30, 1932.-*This latter appli-' cation is in turn a division of my application Serial No. 481,349, filed September-ll, 1930, now Patent No. 1,917,255, which was a' continuation-' in-part of my prior application, Serial No. 475,- 622, filed August 15, 1930, nowPatent No. 1,917,- 250.

What I claim as new and desire to protect by Letters Patent of the'United' States is:

l. A sulpho-acetate of a lower molecular weight polyhydric alcohol wherein the hydrogen of one hydroxyl group or the polyhy'dric alcohol'is substituted by a straight chainhigher molecular weight unsaturated aliphatic radical.

2. A sulpho-acetate of a lower molcular weight tri-hydric alcohol wherein the hydrogen of one hydroxyl group of the tri-hydric alcohol is substituted by a straight chain higher molecular weight unsaturated aliphatic radical containing at least six carbon atoms.

3. A sulpho-acetate of a lower molecular weight polyhydric alcohol wherein the hydrogen of one hydroxyl group of the polyhydric' alcohol is substituted by a straight chain higher molecular weightunsaturated aliphatic radical containing.

eighteen-carbon atoms.

AVA sulpho-acetate .of. a glycol wherein the hydrogen of one hydroxyl group of the glycol is substituted by a straight chain higher molecular weight unsaturated: aliphatic radical.

-5. A derivative of a lower molecular weight tri-hydric alcohol,-.the hydrogen of only one hydroxyl group of which is substituted by a sulphoacetyl radical, andra hydrogen of only one hydroxyl' group of the.tri-hydric alcohol is substituted by a straight chain higher molecular weight unsaturated aliphatic radical.

tea-derivative of a lower molecular weight polyhydric alcohol, the hydrogen of only one hydrcxyl group of which is substituted by a sulphcacetyl radical. and a hy ogen of only one hydroxyl group of the polyhydric alcohol is substituted-by a straight chain higher molecular weight'unsaturatedaliphatic radical containing eightee'ncarbon atoms.

*I. A chemical compound corresponding to the formula o R-C-CHr-SO wherein'rY is an alkali metal, and R is a lower molecular weight polyhydric-alcohol radical in whichthe hydrogen of one hydroxyl group is substitutedJby a higher molecular weight straight chain unsaturated aliphatic radical containing eighteen carbon atoms.

' 8. A carboxylic ester of sulpho-acetic acid. the sulphonic group of which is'unesterified, wherein the radical esterified with the sulpho-aoetic acid is a glycol radical containing a straight chain unsaturated aliphatic radical containing eighteen carbon atoms.

'- BENJAMIN R. HARRIS. 

